JPH03215862A - Photosensitive resin composition - Google Patents

Abstract

PURPOSE:To obtain the positive type photoresist compsn. having a high resolving power by incorporating a specific compd. and alkaline-soluble novolak resin into the photosensitive resin compsn. CONSTITUTION:The positive type photoresist compsn. which can form resist patterns of the sectional shape having a high aspect ratio in patterns of <=1mum line width is obtd. by using the photosensitive resin compsn. contg. the compd. expressed by general formula (A) and the alkaline-soluble novolak resin. The alkaline-soluble novolak resin is obtd. by subjecting 0.6 to 1.0mol aldehydes per 1mol phenols to addition condensation in the presence of an acidic catalyst. The using ratio of the photosensitive material and the alkaline-soluble novolak resin is 5 to 100pts.wt. photosensitive material per 100pts.wt. novolak resin. The residual film rate is extremely inferior if this using ratio is below 5pts.wt. and the degradation in the sensitivity and the solubility in solvents is resulted when the rate exceeds 100pts.wt.

Description

[Detailed Description of the Invention] <Industrial Application Field> The present invention is directed to the use of ultraviolet rays, deep ultraviolet rays, The present invention relates to a photosensitive resin composition that is sensitive to radiation.

More specifically, the present invention relates to a photoresist, and particularly to a photoresist composition for microfabrication that has high resolution and sensitivity, and a good pattern cross-sectional shape.

The photoresist of the present invention is coated onto a substrate such as a semiconductor wafer, glass, ceramics, or metal to a thickness of 0.5 to 3 μm by spin coating or roller coating. Thereafter, it is heated and dried, and a circuit pattern or the like is printed by irradiating ultraviolet rays through a mask and developed to form a positive image.

Further, by etching this positive image as a mask, a pattern can be processed on the substrate. Typical application fields include the manufacturing process of semiconductors such as ICs, the manufacturing of circuit boards such as liquid crystals and thermal heads, and other application processes.

<Conventional technology> As a positive-type photoresist composition, a composition containing an alkali-soluble resin and a nano-and compound as a photosensitive material is generally used.
/ Borac-type 7-functional 7-ru resin / Na7-toquinone diazide substituted compound” USP No. 3,666.473, USP
-4.1 1 5, 1 2 8 and USP-4.1
7 3.470, etc., and the most typical composition, ``Novolac resin more powerful than cresol-formaldehyde/trihydroxybenzo7enone-1,1-na7toquinonediazide sulfonic acid ester'', is given by Thompson ``
Introduction to Microringura 7i J
(L.F. Thompson [Introdu
ction to Mierolitho-gr.
apl+yJ) (ACS Publishing, No. 219, P11
2-121).

7 Volac resin as a binder is particularly suitable for this application because it can be dissolved in aqueous alkaline solutions without swelling and also provides high resistance to plasma etching, especially when the resulting image is used as an etching mask. Useful. In addition, the sodium quinone diazide compound used in photosensitive materials itself acts as a dissolution inhibitor that reduces the alkali solubility of the 7 volcanic resin, but when it is decomposed by light irradiation, it produces alkali-soluble substances. It is unique in that it works to increase the alkali solubility of novolak resins, and because of its large property change in response to light, it is particularly useful as a photosensitive material for positive type photoresists.

From this point of view, many positive type 7 photoresists containing 7 volac resin and 7 quinone diazide photoresists have been developed and put into practical use, and are suitable for line width processing from about 1.5 μm to 2 μm. We have achieved sufficient results.

<Problems to be solved by the present invention> However, as the degree of integration of integrated circuits continues to increase,
In the manufacture of semiconductor substrates such as SI, it has become necessary to process ultra-fine patterns having line widths of 1 μm or less. In such applications, a photoresist with particularly high resolution, high pattern shape reproducibility to accurately copy the shape of the exposure mask, and high sensitivity from the viewpoint of high productivity is required, and the above-mentioned positive type photoresist manufactured by Juu U.S. The reality is that this cannot be done.

Therefore, it is an object of the present invention to provide (1) a positive photorenost composition with high resolution, and (2) a body that accurately reproduces mask dimensions over a wide range of mask line widths, particularly in the manufacture of semiconductor devices. type photoresist composition, (3) in a pattern with a line width of 1 μII or less,
(4) A positive photoresist composition capable of producing a resist pattern with a cross-sectional shape having a high aspect ratio; (4) A positive photoresist composition capable of producing a pattern in which the cross-sectional sidewall of the pattern is nearly vertical; (5) Wide. An object of the present invention is to provide a Bono type 7-year-old photoresist composition having a good development latitude; (6) a positive type photoresist composition in which the obtained resist image has excellent heat resistance.

<Means for Solving the Problems> The inventors of the present invention have completed the present invention as a result of careful study and attention to the above-mentioned characteristics.

That is, the object of the present invention has been achieved by a photosensitive resin composition characterized by containing a compound represented by the following general formula (A) and an alkali-soluble resin.

22, R, -R, each independently hydrogen, hydroxyl group, halodane, alkyl group, alkoxy group, aralkyl group, aryl group, amine 7 group, mo/alkylamino 7 group, dialkylamino group, alkylcarbamoyl group, Arylcarbamoyl group? Lukylsul 7 Amoyl group, carboxyl group, sia/group, ditro group, acyl group, alkyloxycarbonyl group, aryloxycarbonyl group, acyloxy group, 10D
or -N-RD (R is hydrogen or an alkyl group, D is a 1,2-na-7toquinonediazide-5-sulfonyl group or a 1,2-na-7
toquinonediazide-4sulfonyl group) However, at least one of R+ Rs represents -OD or -N-R, and each D group except D may further have a substituent, R1o- R1 ■
: Each independently represents hydrogen or a lower alkyl group which may have a substituent.

In R1 to R9 of the above general formula [A], the halogen is preferably chlorine, bromine, or iodine, and the alkyl group is methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, or L-butyl. Preferred are alkyl groups having 1 to 4 carbon atoms, such as methoxy, ethoxy, hydroxyethoxy, propoxy, hydroxybroboxy, improboxy, n-
Alfoxy groups having 1 to 4 carbon atoms such as ptoxy, imbutoxy, sec-butoxy, and shibutoxy are preferred; aralkyl groups include benzyl, 7-enethyl, and penzhydryl groups; and aryl groups include 7-enyl, tolyl, and hydroxy. 7enyl, na7thyl groups, etc. are preferred,
Monoalkylamino7 groups include monomethylamino, monoethylami7, mo/propylamino/, monoisopropylamino, mono n-butylamino/, monoisobutylamino, monosec-butylamino7, mo7t-butylamino/, etc. having 1 carbon number. -4 mo/alkylamino7 groups are preferred, and the noalkylamino/groups include dimethylamino, diethylami7, dibrobilami/, diisopropylamino, di-n-butylamino, diisobutylamino, di-See-butylamino/, and no-butylamino/. Preferably, 7 noalkylamides each have an alkyl substituent having 1 to 4 carbon atoms, and examples of the 7 acylami groups include acetylami/, probionylami 7, putyrylami 7, inbutyrylamide/, invalerylamide/, bivalylamide 7, and vanlylamide/. Each carbon number is 2 to 5.
aliphatic substituted acyl amide 7 groups, or aromatic substituted acyl amide groups such as penzoylamino, toluoyl amine/
The alkylcarbamoyl group is preferably a group having 2 to 2 carbon atoms such as methylrubamoyl, ethylrubamoyl, propylrubamoyl, isopropylcarbamoyl, n-butylcarbamoyl, inbutylcarbamoyl, Sec-butylcarbamoyl, and t-butylcarbamoyl. 5
An alkylcarbamoyl group is preferable, and the arylcarbamoyl group is preferably 7enylcarbamoyl, tolylbamoyl group, etc., and the alkylsul7amoyl group is methylsul7amoyl, ethylsul7amoyl, probylsul7amoyl, isoprobylsul7amoyl,
1-4 carbon atoms such as n-butylsul 7-amoyl, sec-butylsul 7-amoyl, t-butylsul 7-amoyl
Preferred are alkylsulfamoyl groups such as arylsul7amoyl groups, 7enylsul7amoyl groups, tolylsul7amoyl groups, etc., and examples of acyl groups include formyl, acetyl, probionyl, butyryl, imbutyryl, valeryl, invaleryl, bivaloyl, etc. An aliphatic acyl group having 1 to 5 carbon atoms or an aromatic acyl group such as benzoyl, toluoyl, salicyloyl, and sodium chloride is preferred, and the alkyloxycarbonyl group includes methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, and improboyl group. Preferred are alkyloxycarbonyl groups having 2 to 5 carbon atoms such as oxycarbonyl, n-butoxycarbonyl, inptoxycarbonyl, See-butoxycarbonyl, and t-butoxycarbonyl, and the aryloxycarbonyl group is preferably 7-enoxycarbonyl. Rubonyl group is preferred, and the acyloxy group is an aliphatic acyloxy group having 2 to 5 carbon atoms such as acetoxy, probionyloxy, butyryloxy, imptyryloxy, valeryloxy, isovaleryloxy, bivaloyloxy, or penzoyloxy, toluoyl group. Aromatic acyl groups such as oxy, na7toyloxy are preferred.

In addition, as the alkyl group of R10-R12, a carbon number 1 such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, see-butyl, t-butyl, etc.
~4 alkyl groups are preferred.

The compound represented by the general formula (A) has the general formula (B) 22, R13R21: each independently hydrogen, hydroxyl group, halodane, alkyl group, alkoxy group, aralkyl group, aryl group, amide group, /alkylamino group, sialkylamino group, alkyl-11ylcarbamoyl group, arylcarbamoyl group, alkylsul7amoyl group, carboxyl group, cyano group, nitro group, acyl group, alkyloxy carbonyl group, ゜-lyloxy Carbonyl group and acyloxy group may further have a substituent.

However, at least one of R+3 R21 is a hydroxyl group,
Amii7 group or monoalkylamino group.

R22-R24: each independently hydrogen or a lower alkyl group which may have a substituent.

A derivative of 7 enyl ingone represented by and 1,2-na 7
It can be easily synthesized by condensing diazido 5 (or/and -4)-sulfonyl chloride.

The compound represented by general formula (B) is, for example, described in J. Pos
The method of psil et al. (CollectionCzecl+
oslov. CI+em. Com+nun. IVol.
36, (1971) P1986-1994).

-12- - Specific examples of compounds represented by shell formula (B) include 1-
(4-hydroxy7enyl)-1.3.3. 1-(4-hydroxy-7)
enyl)-1.3,3,-}limethyl-5,6-dihydroxyingne, 1-(3.4-dihydroxy7enyl)-1.3.3,-}limethyl-6-hydroxyingne, 1 = (3.4dihydroxy7enyl)-1.3,
3,1 trimethyl-5,6-dihydroxyingne, 1
-(3-hydroxy7enyl)-1.3,3. ,-}limethyl-6-dihydroxyingne, 1-(3-hydroxy7enyl)-1,3,3,monotrimethyl-5-hydroxyingne, 1-(2-hydroxy7enyl)-1
．． 3,3,T}limethyl-4-hydroxyindan, 1
-(2-hydroxy7enyl)-1.3.3,-}limethyl-7-hydroxyingen, 1-(2.3-dihydroxy7enyl)-1,3,3,monotrimethyl-4,
5-dihydroxyinfone, 1-(2,3-dihydroxy7enyl)1,3,3,monotrimethyl-6,
7-nohydroxyingone, 1-(2.4-dihydroxy7enyl)1,3,3,-}limethyl-4,6-dihydroxyingne, 1-(2.4-dihydroxy7enyl)
(enyl) L3,3,-}limethyl-5,7-dihydroxyenyl, 1-(3,5-dihydroxy7enyl)-
1.3,3,-}limethyl-4,6-nohydroxyingen, 1-(3.5-dihydroxy7enyl)1,3
,3,-}limethyl-5,7-dihydroxyingne,
1-(2,3.4-}lihydroxy7enyl)-L3,
3,1-trimethyl-4,5.6-trihydroxyingne, 1- (213.4-} 1jh droxy7enyl)-1.3.3. -trimethyl-5,6.7-}lihydroxyinge, 1-(2-4,5-}lihydroxy-7enyl)-1.3,3,trimethyl-4.6.7-}lihydroxyinge, 1-(2,4,5-}lihydroxy7enyl)-1.3,3,-}limethyl-4.5.7
-}rihydroxyingone, 1- (2,4.6-trihydroxy7enyl)-1.3,3,1-trimethyl-4
．． 5.6-}lihydroxyingne, 1-(3-methyl-415-hydroxy7enyl)-1.3.3.5-tetramethyl-6-hydroxyingne, 1-(3.5dimethyl-
4-hydroxy7enyl)-1.3,3.5,7-pentamethyl-6-hydroxyingne, 1-(4-ami77enyl)-1.3,3,-}limethyl-6-aminoingne, 1- (3.4-diami/7enyl)-1.3
,3,1-trimethyl-5,6-diaminoingne, 1-
(2.3.4-triamino7enyl)-1.3,3,
monotrityl-5,6,7-triaminoingone, 1-
(2,3.4-trihydroxy7enyl)-1.3,
3,1-triethyl-4.5,6-}rihydroxyingon, 1-<2.3.4-}lihydroxy7enyl)-1
．． 3,3,triethyl-5.6.7-trihydroxyingne, 1-(3-methyl-4-hydroxy7enyl)
-1.3.3,-}rimethyl-5. 6. 7-trihydroxyingone, 1-(4-amino7enyl)-L3
,3. -}limethyl-5.6.7-trihydroxyingne, 1-(2.4-dihydroxy7enyl)-1.
3,3,1-trimethyl-4,6-nohydroxy16-indane,1-(2.4-')hydroxy7enyl)-
Examples include, but are not limited to, 1.3,3,-}limethyl-5,7-dihydroxyingne.

The esterification reaction between the polyhydroxy compound or amine/compound represented by the general formula (B) and 1,2-na7toquinonenoazide to 5-sulfonyl chloride or 1,2-na7}4nondiazide 4-sulfonylchlori V is Conventional methods are used.

That is, a predetermined amount of the compound represented by (B) and 1,2--1
-'7} Quinonediazide-5-sulfonyl chloride or 1,2-na7toquinonediazide-4-sulfonyl chloride and a solvent such as dioxane, acetone, methyl ethyl ketone, N-methylpyrrolidone, etc. are charged into a flask, and a basic catalyst, For example, sodium hydroxide} 17um, sodium carbonate, sodium hydrogen carbonate, triethylamine, 4-
Dimethylami7-pyridine, etc. is added dropwise to condense the mixture. The obtained product is washed with water, then dried. A photosensitive material represented by general formula (A) can be prepared by the above method.

In the above-mentioned esterification reaction, a mixture of compounds having different esterification numbers and esterification positions is obtained.

Therefore, the esterification rate referred to in the present invention is defined as the average value of this mixture.

The esterification rate defined in this way can be controlled by the mixing ratio of compound (B), which is a raw material, and 1,2-na-7-cyazide-5 (and/or -4)-monosulfonyl chloride. That is, since substantially all of the added 1,2-na7toquinonediazide-5 (and/or -4) monosulfonyl chloride undergoes an esterification reaction, in order to obtain a mixture with a desired esterification rate, All you have to do is adjust the molar ratio of the raw materials.

The alkali-soluble novolac resin used in the present invention can be obtained by addition-condensing 0.6 to 1.0 moles of aldehydes to 1 mole of phenols under an acidic catalyst. As the phenols, phenol, 0-cresol, di-cresol, p-cresol, xylenol, and the like can be used alone or in combination of two or more. Further, as the aldehyde, formaldehyde, paraformaldehyde, acetaldehyde, halogenated acetaldehyde (for example, chloro, bromo), or fur7al can be used, and as the acidic catalyst, hydrochloric acid, sulfuric acid, formic acid, oxalic acid, acetic acid, etc. can be used. . The thus obtained 7-borac resin having a molecular weight of 1 and OOO~50,000 exhibits alkali solubility.

In the present invention, the ratio of the photosensitive material and the highly soluble novo 2c resin used is 5 to 100 parts by weight, preferably 10 to 50 parts by weight, per 100 parts by weight of the borac resin. If this usage ratio is less than 5 parts by weight, the residual film rate will be severely reduced, and if it exceeds 100 parts by weight, sensitivity and solubility in solvents will be reduced.

In the present invention, the above-mentioned photosensitive materials should be mainly used, but if necessary, ordinary photosensitive materials such as 2,3.4-trihydroxybenzo-7, 2,4.4'-}-rihydroxybenzo 7-enone, 2,4,6-trihydroxybenzo-7-enone, etc. and 1,2-na-7-toquinonediazide-5
(and/or -4) An ester compound with monosulfonyl chloride can be used in combination. In this case, the above (A)
It can be used in an amount of 100 parts by weight or less, preferably 30 parts by weight or less, per 100 parts by weight of the photosensitive material.

The present invention can further contain a polyhydroxy compound to promote dissolution in a developer.

Preferred polyhydroxy compounds include 7-ols, resorcinol, 7-loroglucin, 2,3.4-}+71=droxybenzo-7-ol, 2,3,4.4'-tetrahydroxybenzo-7-ol, These include 2,3,4.3',4'5'-hexahydroxybenzo7enone, acetone-pyrrole condensation resin, and the like.

Examples of the solvent for dissolving the photosensitive material and the alkali-soluble/borac resin of the present invention include ketones such as methyl ethyl ketone and cyclohexanone, alcohol ethers such as ethylene glycol monomethyl ether and ethylene glycol monomethyl ether, dioxane, ethylene glycol dimethyl ether, Ethers such as diethylene glycol dimethyl ether, methyl cellosolve acetate,
-19 Cellosolve esters such as mono-ethyl cellosolve acetate and 2-ethoxybrobionate, fatty acid esters such as methyl lactate, ethyl lactate, butyl acetate! , 1, 1.2-}
Examples include halodane hydrocarbons such as dichloroethylene, and highly polar solvents such as dimethylacetamide, N-methylpyrrolidone, dimethylformamide, and nomethylsulfoxide. These solvents can be used alone or in combination.

The positive photoresist composition of the present invention may contain dyes, plasticizers, adhesion aids, surfactants, and the like, if necessary. Specific examples include dyes such as methyl violet, crystal violet, and malachite green, plasticizers such as stearic acid, acetal resin, 7-hydroxy resin, and alkyd resin, and adhesion aids such as hexamethyldisilazane and chloromethylsilane. and nonyl-7 enoxy(ethyleneoxy)ethanol, octyl-7
There are surfactants such as enoxypoly(ethyleneoxy)ethanol.

-20- After coating the above positive photoresist composition on a substrate (e.g. silicon/silicon dioxide coating) used in the manufacture of precision integrated circuit elements by an appropriate coating method such as a sinter or footer, A good resist can be obtained by exposing through a mask and developing.

The developing solution for the composition for positive photoresis F of the present invention includes inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-probylamine, etc. Primary amines such as diethylamine, di-n-
Secondary amines such as butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, An aqueous solution of alkalis such as cyclic amines such as pyrrole and vivericin can be used. Furthermore, appropriate amounts of alcohols, surfactants, and alkali-soluble aIN may be added to the aqueous solution of the alkalis mentioned above.

<Effects of the Invention> The Bong-type photorenost of the present invention has high resolution, faithful reproducibility, cross-sectional shape of resist image, development latitude, heat resistance,
Excellent storage stability of resist.

<Examples> Examples will be shown below, but the present invention is not limited thereto. Note that % indicates weight % unless otherwise specified.

Examples (1) to (7), Comparative Example (8) (1) Synthesis of photosensitive material a 10 g of the following compound (a), 16.0 g of 2-naphthoquinonenoazido-5-sulfonyl chloride, and 200 ml of acetone were prepared in three amounts. The mixture was poured into a second flask and dissolved uniformly. Then triethylamine/acetone = 6.3g
A mixed solution of /30UaI was added dropwise to the solution, and the mixture was reacted at 25°C for 3 hours. Add the reaction mixture to 1000 ml of 1% aqueous hydrochloric acid solution.
The resulting precipitate was filtered, washed with water, and dried (40°C) to obtain 23.3 g of 1,2-naphthoquinone diand-5-sulfonic acid ester of compound (a').

(2) Synthesis of photosensitive materials 10 g of the following compound (b), 28.6 g of 1,2-na7toquinonenoand-5-sulfonyl chloride, and 3 acetone
00 ml was placed in a three-necked flask and uniformly dissolved.

Then triethylamine/acetone=1 1. ．． 3g
/401II1 mixture was added dropwise to
Allowed time to react. The reaction mixture was diluted with 1% aqueous hydrochloric acid solution (1500 g)
ml, and the resulting precipitate was filtered, washed with water, and dried (4
0°C) to obtain 34.0 g of 1,2-na7toquinonediazide 5-sulfonic acid ester of compound (b').

(3) Synthesis of photosensitive material C 10 g of the following compound (c), 28.6 g of 1,2-na7diacido-5-sulfonyl chloride and 300 ml of a7tone were charged into a 3-neck, 7-rasf vessel and uniformly dissolved. Then 1.3g of triethylamine/acetone-1
/40+nI mixture was gradually added dropwise, and the mixture was heated at 25℃ for 3 hours.
Allowed time to react. The reaction mixture was diluted with 1% aqueous hydrochloric acid solution (1500 g)
The resulting precipitate was filtered, washed with water, and dried (40°C) to obtain the 1,2-na7toquinonediazide-5-sulfonic acid ester of compound (C) 3. 5g
I got it rL.

(4) Synthesis of photosensitive material d 10 g of the following compound (d), 28.6 g of 1,2-na7toquinonediazide-5-sulfonyl chloride, and 300 liters of acetone were placed in a three-necked flask and uniformly dissolved. Next, a mixed solution of 1.1.3 g of triethylamine/acetone/40 tol was gradually added dropwise, and the mixture was reacted at 25°C for 3 hours.

The reaction mixture was poured into 500 μl of 1% aqueous hydrochloric acid fil, and the resulting precipitate was filtered, washed with water, and dried (40°C) to obtain compound (d) 1.2-naphthoquinonenoazide-5.
-Sulfonic acid ester 3 3. 0g I got it.

(5) Synthesis of photosensitive material e The following compound (e) IOH, 23.9 g of 1.2-na-7toquinone dianodo-5-sulfonyl chloride and 3 acetone.
00+nl was charged into a three-necked flask and uniformly dissolved. Next, triethylamine/acetone"9-51?
/40ml of the mixed solution was added dropwise to the solution, and the mixture was reacted at 25°C for 3 hours. Add the reaction mixture to 1500 ml of 1% aqueous hydrochloric acid solution.
The precipitate formed was filtered, washed with water, and dried (at 40°C).
) to obtain 34+ 3 g of 1,2-na7toquinone cyazide-5-26-sulfonic acid ester of compound (e).

(6) Synthesis of photosensitive material f The following compound (ilOg, 25.1 g of 1,2-na7toquinonenoazido-5-sulfonyl chloride and 30 g of acetone)
0 ml was placed in a three-necked flask and dissolved uniformly. Then triethylamine/acetone=9.9g/40a
+ Remove l mixture! / and reacted at 25°C for 3 hours. The reaction mixture was poured into 1500 anl of 1% aqueous hydrochloric acid solution, and the resulting precipitate was filtered off, washed with water, and dried (40°C).
30.7 g of 1,2-na7toquinonediazide-5-sulfonic acid ester of compound (f) was obtained.

(7) Synthesis of photosensitive material g 10 g of the following compound (g), 38.8 g of 1,2-na7toquinonediazide-5-sulfonyl chloride, and 3 acetone
00 ml was placed in a three-necked flask and uniformly dissolved.

Then triethylamine/acetone=1 5.3g/
A mixed solution of 40 ta I was added dropwise to the solution, and the mixture was reacted at 25° C. for 3 hours. The reaction mixture was diluted with 1% aqueous hydrochloric acid solution 1500+n
The precipitate formed was filtered, washed with water, and dried (40
℃) to obtain 42.2 g of 1,2-na7toquinonediazide 5-sulfonic acid ester of <g) compound.

(8) Synthesis of photosensitive material I1 (comparative example) 2,3,4,4'-tetrahydroxybenzo7enone 7
．． A three-necked flask was charged with 85 g of 1,2-na-7toki/nnoazido-5-sulfonyl chloride, 30 g, and 300 ml of acetone, and uniformly dissolved.

27, then triethylamine/7 setone = 11.3g/30
The +1 mixed solution was added dropwise to the solution, and the mixture was reacted at 25° C. for 3 hours. The reaction mixture was poured into 1500 ml of a 1% aqueous hydrochloric acid solution, and the resulting precipitate was filtered, washed with water, and dried (40°C) to give 2,3,4,4'-tetrahydroxybenzo 7-ether/
Synthesis of 1,2-na-7-toquinone noazido-5-sulfonic acid ester 27.5(9)/borac resin (C) 11-cresol 40g% p-cresol 60g, 37%
49.5 g of formalin aqueous solution and 0.05 g of oxalic acid were placed in a three-necked flask, heated to 100° C. with stirring, and reacted for 7 hours. After the reaction, the reaction mixture was cooled to room temperature and the pressure was reduced to 30 mHg.

Next, the temperature was raised to 150° C. to remove water and unreacted monomers. The obtained novolak resin (C) had a weight average molecular weight of 7,000 (28-28 polystyrene!).

(10) /Synthesis of Borac resin (D) Except for using If-cresol 7og Sp-cresol 20g (
9) and how/Volacic resin (D> was synthesized. The obtained novolac resin (D) had a weight average molecular weight of 93.
00 (polystyrene equivalent).

(11) Preparation and evaluation of positive type 7-year-old photoresist compositions
The cresol/borak resin obtained in 9) or (10) was dissolved in 18 g of ethyl lactate at the ratio shown in Table 1, and 0.2
It was filtered using a μ microfilter to prepare 7 otoresist compositions.

This photoresist was applied to a silicon wafer using a sinter, and heated at 90℃ for 3 hours in a convection oven under a nitrogen atmosphere.
After open drying for 0 minutes, a resist film having a thickness of 1.2 μm was obtained.

A reduction projection exposure device (FPA-1 manufactured by Canon Inc.) was applied to this film.
550), heated at 110° C. for 1 minute using a vacuum adsorption type hot plate, developed with a 2.38% aqueous solution of tetramethylammonium hydroxide for 1 minute, washed with water for 30 seconds, and dried. The resist pattern of the silicon wafer thus obtained was observed with a scanning electron microscope and the resist was evaluated. The results are shown in Table-1.

Sensitivity is 0. It was defined as the reciprocal of the exposure amount for reproducing a mask pattern of 7 μm, and was expressed as a relative value of the sensitivity of Comparative Example 1.

The residual film rate was expressed as a percentage of the ratio of the unexposed area before and after development.

The resolution represents the limit resolution at an exposure amount that reproduces a mask pattern with a gloss of 0.7 μ.

Heat resistance was determined by exposing a silicon wafer on which a resist pattern was formed in a convection oven for 30 minutes, and indicating the temperature at which the pattern did not deform.

The shape of the resist pattern was expressed by the angle (0) between the resist wall surface and the plane of the silicon wafer in the cross section of the 0.7 μm resist pattern.

As can be seen, the renosts using the photoreceptors a"'-g of the present invention were particularly excellent in resolution and resist shape.

The photosensitive materials of the present invention also have excellent solubility in ethyl cellosolve acetate, and resist composition solutions using these photosensitive materials showed no precipitation even when left at 40°C for 30 days. After the Lennost composition solution using photosensitive material 1) of Example was left to stand under the same conditions, precipitation of a precipitate was observed.

Example 8 Photosensitive material co. synthesized in Example 3. 91g and 3.65g of the novolak resin synthesized in Synthesis Example 10. to ethyl lactate13.
A resist composition was prepared by dissolving the solution in 54 g and filtering through a 0.2 μm microfilter.

This resist composition was coated on a silicon wafer with a 2500A oxide film using a sinter, and dried at 80°C for 90 seconds on a vacuum adsorption hot plate in a nitrogen atmosphere to form a resist film with a thickness of 1.2 μW. Obtained. Next, after exposing through a test chart mask using a reduction projection exposure device made by Canon, 12
The resist pattern was baked for 0'C I minutes, developed for 1 minute with a 2.38 weight 1% aqueous solution of tetramethylammonium hydroxide, and rinsed with ion-exchanged water to obtain a resist pattern. The range pattern obtained in this way is (11
) was evaluated using the same method. However, heat resistance was evaluated by baking a silicon wafer having a resist pattern at a predetermined temperature for 4 minutes on a vacuum suction type hot plate, and measuring the temperature at which the resist pattern began to deform.

At this time, the relative sensitivity was 1.22, the residual film rate was 99.2%, the heat resistance was 130° C., and the resolution was 0.50 μω.

Examples 9 to 11 A cresol novolak resin synthesized from the photosensitive materials of Synthesis Examples 2, 5, and 7, 45% by weight of p-cresol, 55% by weight of p-cresol, and formalin (molecular weight 7,200 in terms of polystyrene) ) and a solvent in the ratios shown in Table 2, a resist composition was prepared and evaluated in the same manner as in Example 8. The results are shown in Table-2.

As can be seen from these results, the 7 photoresist of the present invention has excellent sensitivity, resolution, film retention rate, and heat resistance.
Even after being left at 0°C for 30 days, no precipitate was observed in the resist solution.

Claims (1)

[Scope of Claims] A photosensitive resin composition characterized by containing a compound represented by the following general formula (A) and an alkali-soluble resin. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(A) R_1-R_9: Each independently hydrogen, hydroxyl group, halogen, alkyl group, alkoxy group, aralkyl group, aryl group, amino group, monoalkylamino group, dialkylamino group , alkylcarbamoyl group, arylcarbamoyl group, alkylsulfamoyl group, carboxyl group,
Cyano group, nitro group, acyl group, alkyloxycarbonyl group, aryloxycarbonyl group, acyloxy group, -
OD or ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (R represents hydrogen or an alkyl group, D represents a 1,2-naphthoquinonediazide-5-sulfonyl group or a 1,2-naphthoquinonediazide-4-sulfonyl group), but , at least one of R_1-R_9 is -OD
Or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and D
Each group except for may further have a substituent. R_1_0-R_1_2: each independently represents hydrogen or a lower alkyl group which may have a substituent.